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Культура Документы
By
Arman Mohammed Abdalla Ahmed
B.Sc in Plastic Engineering Technology, 2005
Sudan University of Science and Technology -College of
Engineering
Supervisor:
Dr. Mustafa Abbas Mustafa
January / 2010
ﻗﺎل ﺗﻌﺎﻟﻰ :
ﻻ
ﺖ َر ﱠﺑ َﻨ ﺎ َ
ﺴ َﺒ ْ
ﻋَﻠ ْﻴﻬَﺎ ﻣَﺎ ا ْآ َﺘ َ
ﺖ َو َ
ﺴ َﺒ ْ
ﺳ َﻌﻬَﺎ َﻟﻬَﺎ ﻣَﺎ َآ َ
ﻻ ُو ْ
ﻒ اﻟﱠﻠ ُﻪ َﻧﻔُﺴًﺎ إ ﱠ
ﻻ ُﻳ َﻜِﻠّ ُ
)َ
ﻋﻠَﻰ
ﺣ َﻤ ْﻠ َﺘ ُﻪ َ
ﻋَﻠ ْﻴﻨَﺎ ِإﺻْﺮًا َآﻤَﺎ َ
ﻞ َ
ﺤ ِﻤ ْ
ﻄ ْﺄﻧَﺎ َر ﱠﺑﻨَﺎ وَﻵ َﺗ ْ
ﺧَ
ﺧ ْﺬﻧَﺎ إِن ﱠﻧﺴِﻴﻨَﺎ َأ ْو َأ ْ
ُﺗﺆَا ِ
ﻏ ِﻔ ْﺮ َﻟ َﻨ ﺎ
ﻋﱠﻨ ﺎ وَا ْ
ﻒ َ
ﻋ ُ
ﻻ ﻃَﺎ َﻗ َﺔ َﻟﻨَﺎ ِﺑ ِﻪ وَا ْ
ﺤﻤﱢﻠﻨَﺎ ﻣَﺎ َ
ﻻ ُﺗ َ
ﻦ ﻣِﻦ َﻗ ْﺒِﻠﻨَﺎ َر ﱠﺑﻨَﺎ َو َ
اﱠﻟﺬِﻳ َ
ﻦ(
ﻋﻠَﻰ اﻟ َﻘ ْﻮ ِم ا ْﻟﻜَﺎ ِﻓﺮِﻳ َ
ﺼ ْﺮﻧَﺎ َ
ﻻﻧَﺎ ﻓَﺎﻧ ُ
ﺖ َﻣ ْﻮ َ
ﺣ ْﻤﻨَﺎ أَﻧ َ
وَا ْر َ
i
Dedication
,,,,,,,,,,,,,,,,,,,,
TÜÅtÇ
ii
Acknowledgement
I would like to thank the University of Khartoum and to express my
sincere gratitude to my supervisor Dr. Mustafa Abbas Mustafa. I would
like to acknowledge his unlimited efforts in guiding and following up the
thesis progress, and specially his spirit – raising encouragement.
As many people have contributed constructively to this work. I would
like to thank them all and in particular the people of University of
Khartoum - Department of Chemical Engineering - Unit Operations lab,
who provided me with the necessary information to rehabilitate the batch
reactor. I owe special thanks to every body who contributed to this
thesis directly or indirectly.
TÜÅtÇ
iii
Contents
Description Page
اﻵﻳﺔ اﻟﻜﺮﻳﻤﺔ i
Dedication ii
Acknowledgement iii
Table of contents iv
Abstract vi
اﻟﻤﺴﺘﺨﻠﺺ viii
List of figures ix
List of tables xii
Abbreviations and nomenclature xv
CHAPTER ONE: INTRODUCTION
1.1 Background 1
1.2 Objectives 2
CHAPTER TWO: LITERATURE REVIEW
2.1 Description of reactors 3
2.2 The general mole balance equation 7
2.3 Batch reactor design equation 9
2.4 The reaction order and the rate law 11
2.4.1 Power law models 11
2.4.2 The reaction rate constant 12
2.5 Examples of reaction rate laws 14
2.6 Collection and analysis of rate data 17
2.6.1 Differential method of analysis 17
2.6.2 Methods for finding -dCA/ dt from concentration time data 19
2.6.3 Integral method of analysis 20
2.6.4 Comparison between differential and integral methods 21
2.7 Saponification: A Case Study 22
CHAPTER THREE: EQUIPMENT, MATERIALS & METHODS
3.1 Introduction 23
3.2 Equipment 23
iv
3.3 Materials 26
3.4 Methods 27
3.4.1 The Algorithm for kinetic evaluation of Saponification reaction 27
3.4.2 General consideration for Saponification Experiments 28
3.4.3 Analysis Procedure for Saponification Experiments 28
3.4.4 Titration Method 28
3.4.5 Experiment A: Determination of concentration dependency factor
for caustic soda 31
3.4.6 Experiment B: Determination of concentration dependency factor
for Ethyl Acetate 37
3.4.7 Experiment C: Determination of dependency factor
for temperatures 43
CHAPTER FOUR : RESULTS & DISCUSSION
4.1 Results 53
4.1.1 Experiment A 53
4.1.2 Experiment B 57
4.1.3 Experiment C 61
4.2 Discussion 65
4.2.1 Discussion Experiment A 65
4.2.2 Discussion Experiment B 78
4.2.3 Discussion Experiment C 79
4.2.4 Discussion Activation Energy 80
CHAPTER FIVE: CONCLUSION & RECOMMENDATIONS
5.1 Conclusion 84
5.2 Recommendations 84
REFERENCES
References 85
APPENDIXES
Appendix A : Materials Safety Data Sheet (MSDS) 86
Appendix B : CHEMCAD Software (Saponification Reaction Simulation) 89
Appendix C : Rate constant versus Temperatures in Saponification
Literature Values 95
v
Abstract
Knowledge of kinetic parameters is of extreme importance for the
chemical engineer prior to design of chemical reactors. This research
focuses on the study of the kinetics of the saponification reaction
between sodium hydroxide and ethyl acetate in a batch reactor.
To achieve this, the batch reactor available at the unit operation
laboratory (Department of Chemical Engineering, University of
Khartoum) had been repaired and modified to suit the experimental
procedures. The maintenance of the reactor includes change of bearing
and bushes. The modification was made on the motion transmission from
the electric motor to the agitator and on the temperature control system
where a digital thermometer was used.
Prior to the kinetic study, two methods were tried for the temperature
control. The first method used an electric heater plus a cooling jacket
around the reactor but failed to precisely control the temperature. The
second method used consists of a water bath of controlled temperature
where the reactants are heated to the required temperature before they
were fed to the reactor which was also heated to the same temperature
using the water jacket. This method was successful in achieving a tight
control of the temperature, thus ensuring isothermal conditions.
The reactions kinetics was studied through initially studying caustic
soda concentrations dependency using an excess of ethyl acetate while
maintaining isothermal conditions .Then the concentration dependency
of ethyl acetate was evaluated using equal concentrations of reactants
before operating at various condition to evaluate the temperature
dependency.
Analytical mathematical and computer methods were used to analyze
the experimental observations and data. The results obtained (of
evaluated kinetic parameters) showed, a clear agreement with the values
vi
from literature. Improved numerical accuracy has been shown in some
cases to result as the use of polynomial fit relative to finite difference
method.
It is recommended that future work focuses on fully automating the
batch reactor using appropriate hardware and software (Labview)
components.
vii
ﻣﺴﺘﺨﻠﺺ اﻟﺒﺤﺚ
ﺑﺎﻟﻨ ﺴﺒﺔ ﻟﻠﻤﻬﻨ ﺪس اﻟﻜﻴﻤﻴ ﺎﺋﻰ ﻣ ﻦ اﻟﻤﻬ ﻢ ﻣﻌﺮﻓ ﺔ اﻟﻤﺘﻐﻴ ﺮات اﻟﻜﻴﻨﻤﺎﺗﻴﻜﻴ ﻪ )ﺣﺮآﻴ ﺔ اﻟﺘﻔﺎﻋ ﻞ( ﻗﺒ ﻞ
اﻟﺸﺮوع ﻓﻰ ﺗﺼﻤﻴﻢ اﻟﻤﻔﺎﻋﻞ اﻟﻜﻴﻤﻴﺎﺋﻰ .ﻳﺮآﺰ هﺬا اﻟﺒﺤﺚ ﻋﻠﻰ دراﺳ ﺔ ﺣﺮآﻴ ﺔ ﺗﻔﺎﻋ ﻞ اﻟﺘ ﺼﺒﻦ ﻣ ﺎ
ﺑﻴﻦ هﻴﺪروآﺴﻴﺪ اﻟﺼﻮدﻳﻮم واﺳﺘﺎت اﻹﻳﺜﻴﻞ ﻓﻰ ﻣﻔﺎﻋﻞ اﻟﻮﺟﺒﻪ )اﻟﺤﻠﻪ(.
ﻹﻧﺠﺎز هﺬا ،اﻟﻤﻔﺎﻋ ﻞ اﻟﻤﻮﺟ ﻮد ﻓ ﻰ ﻣﻌﻤ ﻞ اﻟﻌﻤﻠﻴ ﺎت اﻟﻤﻮﺣ ﺪ )ﻗ ﺴﻢ اﻟﻬﻨﺪﺳ ﻪ اﻟﻜﻴﻤﻴﺎﺋﻴ ﻪ ،ﺟﺎﻣﻌ ﺔ
اﻟﺨﺮﻃﻮم ( ﺗﻢ إﺻﻼﺣﻪ وﺗﻌﺪﻳﻠﻪ ﻟﻤﻼﺋﻤ ﺔ ﻃ ﺮق اﻟﺘﺠ ﺎرب اﻟﻤ ﺴﺘﺨﺪﻣﻪ .اﻟ ﺼﻴﺎﻧﺔ ﻟﻠﻤﻔﺎﻋ ﻞ اﺷ ﺘﻤﻠﺖ
ﻋﻠﻰ ﺗﻐﻴﻴﺮ اﻟﺒﻠﻰ واﻟﺠﻠﺐ .واﻟﺘﻌﺪﻳﻼت اﻟﺨﺎﺻﻪ ﺑﻨﻘ ﻞ اﻟﺤﺮآ ﻪ ﻣ ﻦ اﻟﻤﺤ ﺮك اﻟﻜﻬﺮﺑ ﺎﺋﻰ اﻟ ﻰ ﺧ ﻼط
اﻟﻤﻔﺎﻋﻞ وآﺬﻟﻚ ﺗﻐﻴﻴﺮ ﻧﻈﺎم اﻟﺘﺤﻜﻢ ﻓﻰ درﺟﺔ ﺣﺮارة اﻟﻤﻔﺎﻋﻞ ﺣﻴﺚ اﺳﺘﺨﺪم ﻣﻘﻴﺎس ﺣﺮارﻩ رﻗﻤﻰ .
ﻗﺒﻞ دراﺳ ﺔ ﺣﺮآﻴ ﻪ اﻟﺘﻔﺎﻋ ﻞ ،اﺧﺘﺒ ﺮت ﻃﺮﻳﻘﺘ ﺎن ﻟﻠ ﺘﺤﻜﻢ ﻓ ﻰ درﺟ ﺔ ﺣ ﺮارﻩ اﻟﻤﻔﺎﻋ ﻞ .اﻟﻄﺮﻳﻘ ﻪ
اﻻوﻟﻰ اﺳﺘﺨﺪم ﺳ ﺨﺎن آﻬﺮﺑ ﺎﺋﻰ ﺑﺎﻻﺿ ﺎﻓﻪ اﻟ ﻰ ﻗﻤ ﻴﺺ ﺗﺒﺮﻳ ﺪ ﺣ ﻮل اﻟﻤﻔﺎﻋ ﻞ وﻟﻜﻨﻬ ﺎ ﻟ ﻢ ﺗ ﻨﺠﺢ ﻓ ﻰ
ﺿﺒﻂ درﺟﺔ اﻟﻤﻔﺎﻋﻞ ﺑﺎﻟﺪﻗﻪ اﻟﻤﻄﻠﻮﺑﻪ .اﻟﻄﺮﻳﻘﻪ اﻟﺜﺎﻧﻴﻪ اﺳ ﺘﺨﺪم ﺣﻤ ﺎم ﻣ ﺎﺋﻰ ﻟ ﻪ درﺟ ﺔ ﺣ ﺮارﻩ ﺛﺎﺑﺘ ﻪ
ﺣﻴ ﺚ ﻳ ﺘﻢ ﻓﻴ ﻪ ﺗ ﺴﺨﻴﻦ اﻟﻤ ﻮاد اﻟﻤﺘﻔﺎﻋﻠ ﻪ وﻧﻔ ﺲ اﻟﻤ ﺎء اﻟﻤ ﺘﺤﻜﻢ ﻓ ﻰ درﺟ ﺔ ﺣﺮارﺗﻬ ﺎ ﺗ ﺴﺘﺨﺪم داﺧ ﻞ
اﻟﻘﻤﻴﺺ ﺣﻮل اﻟﻤﻔﺎﻋﻞ .وهﻰ ﻃﺮﻳﻘﻪ ﻧﺎﺟﺤﻪ ﻟﻠﺤﺼﻮل ﻋﻠﻰ درﺟﺔ ﺣﺮارﻩ ﺛﺎﺑﺘﻪ.
ﺗﻢ دراﺳﺔ ﺣﺮآﻴﺔ اﻟﺘﻔﺎﻋ ﻞ اﻟﻜﻴﻤﻴ ﺎﺋﻰ ﺑﺪراﺳ ﺔ اﻹﻋﺘﻤ ﺎد ﻋﻠ ﻰ ﺗﺮآﻴ ﺰ اﻟ ﺼﻮدا اﻟﻜﺎوﻳ ﻪ وإﺳ ﺘﺨﺪام
ﻓﺎﺋﺾ ﻣﻦ أﺳﺘﺎت اﻹﻳﺜﻴﻞ وذﻟﻚ ﻋﻨﺪ ﺛﺒﻮت درﺟﺔ اﻟﺤﺮارﻩ .ﺛﻢ دراﺳﺔ اﻹﻋﺘﻤﺎد ﻋﻠﻰ ﺗﺮآﻴﺰ اﺳ ﺘﺎت
اﻹﻳﺜﻴﻞ ﺑﺈﺳﺘﺨﺪام ﺗﺮاآﻴﺰ ﻣﺘﺴﺎوﻳﻪ ﻣﻦ اﻟﻤﺎدﺗﻴﻦ وﻣﻦ ﺛﻢ درس اﻋﺘﻤﺎد اﻟﺘﻔﺎﻋ ﻞ ﻋﻠ ﻰ درﺟ ﺔ اﻟﺤ ﺮارﻩ
ﺑﺘﻐﻴﺮ درﺟﺔ اﻟﺤﺮارﻩ .
اﺳ ﺘﺨﺪﻣﺖ اﻟﻄﺮﻳﻘ ﻪ اﻟﺮﻳﺎﺿ ﻴﻪ ﻟﻠﺘﺤﻠﻴ ﻞ وﻃ ﺮق اﻟﺤﺎﺳ ﻮب ﻟﺘﺤﻠﻴ ﻞ ﻧﺘ ﺎﺋﺞ اﻹﺧﺘﺒ ﺎرات اﻟﻤﻌﻤﻠﻴ ﻪ.
اﻟﻨﺘ ﺎﺋﺞ اﻟﻤﺘﺤ ﺼﻞ ﻋﻠﻴﻬ ﺎ)ﻟﻘ ﻴﻢ ﻣﺘﻐﻴ ﺮات ﺣﺮآﻴ ﺔ اﻟﺘﻔﺎﻋ ﻞ( ﺗﺘﻔ ﻖ ﻣ ﻊ اﻟﻘ ﻴﻢ اﻟﻤﻮﺟ ﻮدﻩ ﻓ ﻰ اﻟﻤﺮاﺟ ﻊ
اﻟﻌﻠﻤﻴﻪ .آﺬﻟﻚ اﺳﺘﺨﺪﻣﺖ اﻟﻄﺮق اﻟﻌﺪدﻳﺔ ﻟﻠﺤﺼﻮل ﻋﻠﻰ ﺗﻄﺎﺑﻖ ﻣﻊ دوال اﻟﻘﻮى ﻣﺘﻌﺪدة اﻟﺤﺪود .
ﻼ ﺑﺈﺳ ﺘﺨﺪام اﻟ ﺘﺤﻜﻢ اﻷﺗﻮﻣ ﺎﺗﻴﻜﻴﻰ ﻓ ﻰ اﻟﻤﻔﺎﻋ ﻞ وذﻟ ﻚ ﻋ ﻦ ﻃﺮﻳ ﻖ
ه ﺬة اﻟﺪراﺳ ﺔ ﺗﻮﺻ ﻰ ﻣ ﺴﺘﻘﺒ ً
ﺑﺮاﻣﺞ اﻟﺤﺎﺳﻮب وﻣﻠﺤﻘﺎﺗﻪ .
viii
List of figures
NO Description Page
Figure (2.1): Simple batch homogeneous reactor 3
Figure (2.2): Continuous-stirred tank reactor (CSTR) 5
Figure (2.3): Plug-flow tubular reactor (PFR) 6
Figure (2.4): Packed-bed reactor (PBR) 7
Figure (2.5): Balance in system volume 7
Figure (2.6): Calculation of the activation energy 13
Figure (2.7): Zero Order Reaction 14
Figure (2.8): First Order Reaction 15
Figure (2.9): Second Order Reaction equal molar 16
Figure (2.10): Second Order Reaction non equal molar 16
Figure (2.11): Differential method to determine reaction order 18
Figure (2.12): Integral method (the necessary graph for
order guessed) 21
Figure (3.1): Batch reactor with water around it from
thermostat bath 25
Figure (3.2): Withdraw the sample by medical injection , acid with an
indicator in E-flask and the titration unit 30
Figure (3.3): Experiment C Concept Excel program to Plot graph
for 1/CAvs t and Trend (Line) to get k'' 43
Figure (4.1): Experiment A(isothermal at 37.70C) batch (I)
Concentration time data from Experimental in Table (3.6)
and literature values from Appendix B . 53
0
Figure (4.2): Experiment A(isothermal at 37.7 C) batch (I)
Experimental rate of reaction (NaOH) versus its
concentration in Table (3.6) . 54
Figure (4.3): Experiment A(isothermal at 37.70C) batch (II)
Concentration time data from Experimental in
Table (3.6) and literature values from Appendix B. 54
0
Figure (4.4): Experiment A(isothermal at 37.7 C) batch (II)
ix
Experimental rate of reaction (NaOH) versus
its concentration in Table (3.6) . 55
0
Figure (4.5): Experiment A(isothermal at 37.7 C) batch (III)
Concentration time data from Experimental in
Table (3.6) and literature values from Appendix B. 56
Figure (4.6): Experiment A(isothermal at 37.70C) batch (III)
Experimental rate of reaction (NaOH) versus its
concentration in Table (3.6) . 56
0
Figure (4.7): Experiment B (isothermal at 37.7 C) batch (I)
Concentration time data from Experimental in
Table (3.12) and literature values from Appendix B. 57
Figure (4.8): Experiment B (isothermal at 37.70C) batch (I)
Experimental rate of reaction (NaOH) versus its
concentration in Table (3.12) . 58
Figure (4.9): Experiment B (isothermal at 37.70C) batch (II)
Concentration time data from Experimental in
Table (3.12) and literature values from Appendix B. 58
0
Figure (4.10):Experiment B (isothermal at 37.7 C) batch (II)
Experimental rate of reaction (NaOH) versus its
concentration in Table (3.12). 59
Figure (4.11):Experiment B (isothermal at 37.70C) batch (III)
Concentration time data from Experimental in Table (3.12)
and literature values from Appendix B. 60
0
Figure (4.12):Experiment B (isothermal at 37.7 C) batch (III)
Experimental rate of reaction (NaOH) versus its
concentration in Table (3.12). 60
Figure (4.13):Experiment C (at 31.20C) batch (I)
Concentration time data from Experimental and
literature values from Table (3.16). 61
Figure (4.14):Experiment C(at 31.20C) batch (I) Excel program
to plot 1/CA vs t from Table (3.16). 62
0
Figure (4.15):Experiment C (at 37.7 C) batch (II)
x
Concentration time data from Experimental and
Actual fromTable (3.20). 62
0
Figure (4.16):Experiment C (at 37.7 C) batch (II) Excel program
to plot 1/CA vs t from Table (3.20). 63
Figure (4.17): Experiment C (at 45.50C) batch (III)
Concentration time data from Experimental and
Actual Table (3.24). 64
Figure (4.18): Experiment C (at 45.50C) batch (III) Excel program
to plot 1/CA vs t from Table (3.26). 64
Figure (4.19): Experiment A batch (I) data input to poly math program 66
Figure (4.20): Experiment A batch (I) Excel program to plot rate of
reaction (NaOH) versus its concentration
in Table (4.2). 69
Figure (4.21): Experiment A batch (II) data input to poly math program 70
Figure (4.22): Experiment A batch (II) Excel program to plot
rate of reaction (NaOH) versus its concentration
in Table (4.3). 73
Figure (4.23): Experiment A batch (III) data input to poly mat program 74
Figure (4.24): Experiment A batch (III) Excel program to plot
rate of reaction (NaOH) versus its concentration
in Table (4.5). 77
Figure (4.25): Excel plot Activation Energy form Table (4.11) . 81
Figure (4.26): Excel plot Activation Energy for Experiment C batch(I)
and batch(II) from table (4.11). 82
Figure (B.1): CHEMCAD Experiment A concentration time data 89
Figure (B.2): CHEMCAD Experiment A Excel plot log log data
in Table (B.1) 91
Figure (B.3): CHEMCAD Experiment B concentration time data 91
Figure (B.4): CHEMCAD Experiment B Excel plot log log data
in Table (B.2) 94
xi
List of tables
NO Description Page
Table (2.1): Advantages and disadvantages of batch reactor 4
Table (2.3): Advantages and disadvantages of CSTR 5
Table (2.3): Advantages and disadvantages of PFR 6
Table (2.4): Comparison between differential and integral methods 22
Table (3.1): Experiment A Concept Concentration of un reacted NaOH 32
Table (3.2): Experiment A acid base titration 33
Table (3.3):Experiment A batch (I) volume of NaOH use in the titration 34
Table (3.4): Experiment A batch (I) Concentration of unreacted NaOH 35
Table (3.5): Experiment A batch (I) rate of reaction of NaOH 36
Table (3.6): Experiment A the three batches ( t,vtit,Con,rate) of NaOH 36
Table (3.7): Experiment B Concept Concentration of unreacted NaOH 38
Table (3.8): Experiment B acid base titration 39
Table (3.9): Experiment B batch (I) volume of NaOH used
in the titration 40
Table (3.10): Experiment B batch (I) Concentration of unreacted NaOH 41
Table (3.11): Experiment B batch (I) rate of reaction of NaOH 42
Table (3.12): Experiment B the three batches ( t,vtit,Con,rate) of NaOH 42
Table (3.13): Experiment C batch (I) acid base titration 44
Table (3.14): Experiment C batch (I) volume of NaOH used
in the titration 45
Table (3.15): Experiment C batch (I) Concentration of unreacted NaOH 46
Table (3.16): Experiment C batch (I) Concentration of NaOH and its
inverse (Experimental, Actual) 46
Table (3.17): Experiment C batch (II) acid base titration 47
Table (3.18): Experiment C batch (II) volume of NaOH used
in the titration 48
Table (3.19): Experiment C batch (II) Concentration of
unreacted NaOH 49
Table (3.20): Experiment C batch (II) Concentration of NaOH and its
xii
inverse (Experimental, Actual) 49
Table (3.21): Experiment C batch (III) acid base titration 50
Table (3.22): Experiment C batch (III) volume of NaOH used
in the titration 51
Table (3.22): Experiment C batch (III) Concentration of
unreacted NaOH 52
Table (3.24): Experiment C batch (III) Concentration of NaOH and its
inverse (Experimental, Actual) 52
Table (4.1): Experiment A Average Order with respect to (NaOH) 65
Table (4.2): Poly math batch (I) first negative derivative points 69
Table (4.3): Poly math batch (II) first negative derivative points 73
Table (4.4): Poly math batch (III) first negative derivative points 77
Table (4.5): Summary of discussion of experiment A 78
Table (4.6): Experiment B Average overall reaction order with
respect to (NaOH) 78
Table (4.7): Summary of discussion of experiment B 78
Table (4.8): Experiment C rate constant for second order reaction
with respect to (NaOH) 79
Table (4.9): Measuring the temperatures of every sample was
withdraw from reactor 79
Table (4.10): Experiment C reason (1) rate constant for second order
reaction with respect to (NaOH) 80
Table (4.11): Activation Energy Experiment C and Actual or literature
value from Appendix C 81
Table (4.12): Summary discussion of saponification experiments 82
Table (4.13): The comprehension rate equation 83
Table (A.1): Chemical Safety Data for Sodium Hydroxide 86
Table (A.2): Chemical Safety Data for Ethyl acetate 87
Table (B.1): CHEMCAD Experiment A concentration time
data combine with finite difference and Excel 90
Table (B.2): CHEMCAD Experiment B concentration time data
xiii
combine with finite difference and Excel 92
Table (C.1): Rate constant vs Temperatures in Saponification
Literature Values 95
xiv
Abbreviations and Nomenclature
A Frequency factor (litter/mol.sec)
CA Concentration of A after time t (mol/litter)
CA0 Initial concentration of A (mol/litter)
CSTR Continuous stripping tank reactor
E Activity energy (J/mol or cal/mol )
EtAc Ethyl acetate (Ethyl Acetate, CH3COOC2H5 )
Fj Out flow of species j (mol/time)
Fj0 In flow of species j (mol/time)
Gj Rate of generation of species j (mol/time)
HCl Hydrochloric acid (HCl)
K The reaction constant (litter/mol.sec)
MSDS Material safety data sheet
M.W Molecular weight (g/mol)
n Order of reaction (dimensionless)
NA Number of moles of A remain in the reactor (mol)
NA0 Number of moles of A initially in the reactor (mol)
Nj Number of moles of species j (mol)
NaAc Sodium acetate (CH3COONa)
NaOH Sodium hydroxide
PBR Packed bed reactor
PFR Plug flow reactor
R Gas constant (R= 8.314 J/mol.0K)
rj Rate of formation of species j (mol/litter. time)
t Time (sec)
V Volume (litter or ml)
Vtit Volume of NaOH used in titration (ml)
X Conversion (dimensionless)
xv
CHAPTER ONE
INTRODUCTION
1.1. Background
A batch reactor may be described as a vessel in which any chemicals
are placed to react. Batch reactors are normally used in studying the
kinetics of chemical reactions, where the variation of a property of the
reaction mixture is observed as the reaction progresses. Data collected
usually consist of changes in variables such as concentration of a
component, total volume of the system or a physical property like
electrical conductivity. The data collected are then analyzed using
pertinent equations to find desired kinetic parameters.
There is currently a pilot- scale batch reactor at the University of
Khartoum - Department of Chemical Engineering - unit operations lab.
One of the main objectives of this is thesis to rehabilitate and repair this
reactor.
In order to validate this reactor a Saponification Reaction was
chosen, because it is homogeneous (liquid phase reaction) in this case as
constant volume reactor and Safety its reactants and products (Appendix
A: Material Safety Data Sheet (MSDS)).
A saponification is a reaction between an ester and an alkali, such as
sodium hydroxide, producing a free alcohol and an acid salt.
The stoichiometry of the saponification reaction between sodium
hydroxide and Ethyl Acetate is:
CH3COOC2H5 + NaOH Æ CH3COONa + C2H5OH ------------- Eq(1.1)
Saponification is primarily used for the production of soaps.
1
1.2. Objectives
The Repair of batch reactor in University of Khartoum -
Department of Chemical Engineering - Unit Operations Lab.
The validation of the repaired reactor by using a
Saponification reaction and get experimental kinetic data, the
values obtained was compared to values from Literature.
2
CHAPTER TWO
LITERATURE REVIEW
2.1. Description of reactors.
2.1.1 Batch reactor
A batch reactor is used for small-scale operation, for testing new
processes that have not been fully developed, for the manufacture
of expensive products, and for processes that are difficult to
convert to continuous operations. The reactor can be charged (i.e.,
filled) through the holes at the top (Figure 2.1). The batch reactor
has the advantage and also has the disadvantages are shown in
Table2.1.
3
Table 2.1: Advantages and disadvantages of batch reactor
Advantages disadvantages
High conversions can be obtained. High cost of labor per unit of production.
Versatile, used to make many Difficult to maintain large scale
products. production.
Good for producing small Long idle time (Charging & Discharging
amounts. times) leads to periods of no production.
Easy to Clean No instrumentation – Poor product
quality
4
Figure 2.2: Continuous-Stirred Tank Reactor (CSTR)
The Continuous-Stirred Tank Reactor (CSTR) has advantages and the
disadvantages as shown in Table 2.2.
Table 2.2: Advantages and disadvantages of CSTR
Advantages disadvantages
Can be operated at temperatures The conversion of reactant per
between 20 and 450°F and at volume of reactor is the smallest of
pressures up to 100 psi. the flow reactors. Consequently,
Can either be used by itself or as part very large reactors are necessary to
of a series or battery of CSTRs obtain high conversions.
Is relatively easy to maintain good
temperature control since it is well
mixed.
5
assume that the concentration varies continuously in the axial direction
through the reactor. Consequently, the reaction rate, which is a function
of concentration for all but zero-order reactions, will also vary axially.
For the purposes of the material presented here, we consider systems in
which the flow field may be modeled by that of a plug flow profile (e g.
uniform velocity as in turbulent flow), as shown in (Figure 2.3). That is
there is no radial variation in the reaction rate and the reactor is referred
to as a plug-flow reactor (PFR).
6
the surface of the catalyst. Consequently, the reaction rate is based on
mass of solid catalyst W, rather than on reactor volume V.
In the three idealized types of reactors just discussed (batch
reactor, PFR, CSTR), the design equations (i.e... mole balances) were
developed based on reactor volume. The derivation of the design
equation for a packed-bed catalytic reactor (PBR) will be carried out in a
manner analogous to the development of the tubular design equation, we
simply replace the volume coordinate, with the catalyst weight
coordinate W. shown in Figure 2.4.
7
A mole balance on species j at any instant of time t, yields the
following equation:
In − Out + Generation = Accumulation
dN j
Fj0 − Fj + G j = − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.1)
dt
product of the reaction volume ,V. and the rate of formation of species j ,
rj .
V
G j = ∫ r j .dv − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.2)
V
dN j
F j 0 − F j + ∫ r j .dv = − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.3)
dt
From this general mole balance equation we can develop the design
equations for the various types of industrial reactors such as (Batch, PFR,
and CSTR).
In a batch reactor has neither inflow nor outflow of reactants or
products while the reaction is being carried out F j 0 = F j = 0 the resulting
8
If the reaction mixture is perfectly mixed so that there is no variation in
the rate of reaction throughout the reactor volume. We can take r j out of
the integral, integrate and write the mole balance in the form.
dN j
= r j .V − − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.5)
dt
2.3. Batch reactor design equation
In most batch reactors, the longer a reactant stays in the reactor, the
more the reactant is converted to product until either equilibrium is
reached or the reactant is exhausted. Consequently, in batch systems the
conversion X is a function of the time the reactants spend in the reactor.
If N A0 is the number of moles of A initially in the reactor. then the total
number of moles of A that have reacted after a time t is [ N A0 ⋅ X ]
Moles of A reacted
[Moles of A reacted (consumed)] = [Moles of A fed].[ ]
Moles of A fed
[mole of A reacted (consumed)] = [ N A0 ].[ X ] − − − − − − − Eq(2.6)
Now, the number of moles of A that remain in the reactor after a time
t, N A can be expressed in terms of N A0 and X:
N A = N A0 − N A0 ⋅ X
9
dN A
− = − rA .V − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.9)
dt
For batch reactors, we are interested in determining how long to leave
the
reactants in the reactor to achieve a certain conversion X. To determine
this length of time, we write the mole balance Eq(2.8) in terms of
conversion by differentiating Equation (2.7) with respect to time,
remembering that N A0 is the number of moles of A initially present and is
therefore a constant with respect to time.
dN A dX
= 0 − N A0
dt dt
Combining the above with Equation (2.8) yields
dX
− N A0 = rA .V
dt
For a batch reactor, the design equation in differential form is :
dX
N A0 = −rA .V − − − − − − − − − − − − − − − − − − − − − − − − Eq(2.10)
dt
We call Equation (2.10) the differential form of the design equation for
batch reactor because we have written the mole balance in terms of
conversion ,the differential forms of the batch reactor mole balances Eq
(2.5) and Eq(2.10) are often used in the interpretation of reaction rate
data and for reactors with heat effects, respectively. Batch reactors are
frequently used in industry for both gas-phase and liquid-phase reactions.
Liquid-phase reactions are frequently carried out in batch reactors when
small-scale production is desired or operating difficulties, rule out the
use of continuous flow systems.
For a constant-volume batch reactor V = V0 Equation (2.8) can be
arranged into the form Eq(2.11) :
10
1 dN A d ( N A / V0 ) dC A
= = = rA − − − − − − − − − − − − − − − − − − − − − Eq (2.11)
V0 dt dt dt
11
− rA = k A C Aa C Bb − − − − − − − − − − − − − − − − − − − − − Eq(2.13)
12
−E
k A [T ] = Ae RT − − − − − − − − − − − − − − − − − − − − − − Eq(2.15)
Where
A = frequency factor
E = activation energy. J/mol or cal/mol
R = gas constant = 8.3 14 J/mol .oK = 1.987 cal/mol .oK
T= absolute temperature, oK
Postulation of the Arrhenius equation, Equation (2.15), is determined
experimentally calculation of the by carrying out the reaction at several
different temperatures. After taking the natural logarithm of Equation
(2.15) we obtain:
E 1
ln k A = ln A − ( ) − − − − − − − − − − − − − − − − − − − − − − Eq(2.16)
R T
and see that the activation energy can be found from a plot of ln k A as a
function of (1/T)
k A [To ] = Ae RTo
and at a temperature T
13
−E
k A [T ] = Ae RT
This equation says that if we know the specific reaction rate k o (T0 ) at a
temperature T0 , and we know the activation energy, E. we can find the
specific reaction rate k (T ) at any other temperature, T. for that reaction.
2.5. Examples of reaction rate laws
2.5.1. Zero Order Reaction:
o Rate low:
dC A
− rA = − =k
dt
o Separate and integrate:
CA t
∫ − dC
C A0
A = ∫ k dt
0
C A0 − C A = kt − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq(2.18)
o Plot Eq(2.18):
Slope=-k
CA
Time
14
2.5.2. First Order Reaction: A → Products
o Rate low:
dC A
− rA = − = kC A
dt
o Separate and integrate:
− dC A t
CA
∫ C A = ∫0 k dt
C A0
ln(C A0 / C A ) = kt − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq(2.19)
Slope=k
Ln (CA0/CA)
Time
∫ C A2 = ∫0 k dt
C A0
1 1
− = kt − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (2.20)
C A C A0
15
XA
Where C A = C Ao (1 − X A ) , = kC A0 t
1− X A
o Plot Eq(2.20):
Slope=k
1/CA
Time
CB0
Where C A = C Ao (1 − X A ) , M =
C A0
o Plot Eq(2.21):
C B C A0 slope = (C B 0 − C A0 )k
ln( )
C B0C A
Time
Figure 2.10: Second Order Reaction non equal molar
16
2.6. Collection and analysis of rate data
Assume that the rate law is of the form
− rA = k A C αA − − − − − − − − − Eq (2.22)
Batch reactors are used primarily to determine rate law parameters for
homogeneous reactions. This determination is usually achieved by
measuring concentration as a function of time and then using either the
differential, integral method of data analysis to determine the reaction
order, α , and specific reaction rate constant, k A .
However, by utilizing the method of excess, it is also possible to
determine the relationship between − rA and the concentration of other
reactant That is for the irreversible reaction below Equation :
A + B → Products
where a and b are both unknown, the reaction could first be run in an
excess of B so that C B remains essentially unchanged during the course
of the reaction and :
− rA = k A C Aa C Bb = k A C Bb C Aa = k ′C Aa − − − − − − − − − − − − − − − − − − Eq (3.23)
Where
k ′ = k A C Bb ≈ k A C Bb 0 − − − − − − − − − − − − − − − − − − − − − − − − − − Eq (3.24)
17
batch reactor and the concentration recorded as a function of time. By
combining (the mole balance with the rate low given by (Eq 2.22).
dC A
− = k A C αA − − − − − − − − − Eq (2.22)
dt
After taking the natural logarithm of both sides of Equation (2.22)
⎛ dC A ⎞
ln⎜ − ⎟ = ln(k A ) + α ln (C A ) − − − − − − − − − Eq (2.25)
⎝ dt ⎠
⎛ dC A ⎞
Observe that the slope of a plot of ln⎜ − ⎟ as a function of
⎝ dt ⎠
ln (C A ) is the reaction order, α (Figure 2.8 ).
18
2.6.2. Methods for finding − dC A / dt from concentration time data
To obtain the derivative -dCA/dt used in this plot in fig(2.8), we must
differentiate the concentration-time data either numerically or
graphically. We describe two methods to determine the derivative from
data giving the concentration as a function of time. These methods are:
2.6.2.1 Numerical method
Numerical differentiation formulas can be used when the data points in
the independent variable are equally spaced . Such as t1 − t 0 = t 2 − t1 = ∆t :
Time(sec) to t1 t2 t3
Concentration CA0 CA1 CA2 CA3
(mol/lit)
The three-point differentiation formulas
Initial point:
⎡ dC A ⎤ − 3C A0 + 4C A1 − C A 2
⎢ dt ⎥ = 2∆t
− − − − − − − − − − − Eq(2.27)
⎣ ⎦ t =0
Interior points:
⎡ dC A ⎤ (C A(i +1) − C A(i −1) )
⎢ dt ⎥ = − − − − − − − − − − − − − − Eq (2.28)
⎣ ⎦ t =i 2∆t
Last point:
⎡ dC A ⎤ − 3C A( n − 2 ) + 4C A( n −1) − C A( n )
⎢ dt ⎥ = 2∆t
− − − − − − − − Eq(2.29)
⎣ ⎦ t =n
Can be used to calculate dCA/dt . Equations (2.27) and (2.29) are used
for the first and last data points, respectively, while Equation (2.28) is
used for all intermediate data points.
19
2.6.2.2 Polynomial fit
Another technique to differentiate the data is to fit the concentration
time data to an nth-order polynomial:
C A = a 0 + a 1 .t + a 2 .t 2 + a 3 .t 3 + ...... − − − − − − − − − − − Eq ( 2 . 30 )
dC A
= a 1 + 2 a 2 .t + 3 a 3 .t 2 + ....... − − − − − − − − − − − − Eq ( 2 . 31 )
dt
20
Figure 2.12: Integral method (the necessary graph for order guessed)
2.6.4 Comparison between differential and integral methods
By comparing the methods of analysis of the rate data (Table 2.2) .we
note that the differential method tends to accentuate the uncertainties in
the data, while the integral method tends to smooth the data ,there by
disguising the uncertainties in it. In most analyses, it is imperative that
the engineer know the limits and uncertainties in the data. This prior
knowledge is necessary to provide for a safety factor when scaling up a
process from laboratory experiments to design either a pilot plant or full-
scale industrial plant. [1]
21
Table 2.4: Comparison between differential and integral methods. [2]
Integral Method Differential Method
• Easy to use and is recommended for • Useful in complicated cases
testing specific mechanism • Require large and more accurate
• Require small amount of data data
• Involves trial and error • No trial and error
• Cannot be used for fractional orders • Can be used for fractional orders
• Very accurate • Less accurate
22
CHAPTER THREE
EQUIPMENT, MATERIALS & METHODS
3.1. Introduction
To run saponification reaction we need to equipment, materials like
chemical, methods to collect and analyze data.
3.2. Equipment
1. Repaired batch reactor at unit operations lab
The batch reactor was repaired to the model shown in (Figure 3.1).
Firstly, it was contained on parts (electrical heater, Motor, reactor vessel,
Impeller). Impeller was repaired by taking apart it and lubricate it,
thereafter, the maintenance of the reactor includes change of bearing and
pushes the modification was made on the motion transmission from the
electric motor to the agitator and on the temperature control system
where digital thermometer was used , medical injection was withdraw
the samples from reactor.
Two methods were tried for the temperature control, the first
method used an electric heater plus a cooling jacket around the reactor
but it failed to precisely control the temperature according to procedure
below:
One of reactants was placed in reactor vessel , the electrical heater
was opened to heat reactant temperature till reached to above required
temperature about + 0.50C the electrical heater was closed the valve of
cold water was opened to decrease its temperature till reached below
required temperature about -0.50C the valve was closed and opened the
electrical heater again . We Observed in this method the temperature of
reactant was not constant because the reactor put on heater and the heater
it gave heat after we closed it (the temperature of resource was not
constant).The second method used consists of water bath of controlled
23
temperature where the reactants are heated to the required temperature
before they were fed to the reactor which was also heated to the same
temperature using the water jacket , this method was successful to
control the temperature according to procedure below:
One of reactants was placed in reactor vessel ,the switch of thermostat
water bath was set at constant temperature let us say (300C) the valve of
hot water was opened to heat the reactant its temperature was increased
slowly after 20 min the temperature of reactant was reached to above
required temperature (300C) of thermostat bath about 1.20C at last the
temperature of reactant was constant at the (31.2 0C), we observed in this
method the temperature of reactor if the switch was set at an another
values in the thermostat bath (350C, 450C) the constant temperature of
reactor according to this the values (37.70C, 45.50C) respectively in this
case get good results at constant temperatures for reactor(31.20C,
37.70C and 45.50C).
Figure 3.1: water bath of controlled temperature for the batch reactor
24
Figure 3.1: Batch reactor with water around it from thermostat bath
25
3.3. Materials
3.3.1. Chemicals
1. Phenolphthalein
Use as indicator is added to the acid in the E-flask . Causes the
solutions to change color when the acid is neutralized.
2. Hydrochloric Acid (HCl)
Properties: Liquid, Concentration 32 %, M.W 36.46,Wt.per ml at 20 0C
equal 1.189 g/ml
3. Sodium Hydroxide (NaOH)
Properties: Solid Pellets, M.W 40.00
4. Ethyl Acetate(CH3COOC2H5)
Properties: liquid, Concentration 99 %, M.W 88.11, Wt.per ml at 20 0C
equal 0.902 g/ml
5. Distillated Water
Distillated water was Prepared in unit operation lab.
3.3.2. Prepare solution of the reactants
The reactants were prepared through the following procedure:
1. If the solution of reactants was prepared from solid material like
Sodium Hydroxide .
For example when preparing solution of 0.1 M NaOH /litter
The weight taken from the bottle = Morality × M.W = 0.1 × 40 = 4 g − − − − − − Eq(3.1)
26
concentration % × specific gravity× 1000
The moralityof the bottle =
Molecular weight × 100
32 × 1.189 × 1000
= = 10.44 mol / ml − − − − − − − − − Eq(3.2)
36.46 × 100
10.44 mol/ml× volumefrom bottle = 0.1× 1000 → volumefrom bottle = 9.58 ml
Consider − rA = k A C A C B − − − Eq(3.3)
a b
27
Run the experiment at constant temperature to fix k A as described in
groups of Experiments (A & B ) and thus determine the coefficient a
and b respectively .
2. Non isothermal operation
Run the experiment at different temperatures (Experiment C) to see the
28
The steps needed to accomplish this are listed below:
1. Prepare HCl use in the experiments , 0.05M HCl was prepared .
2. 10 mL of the 0.05 M HCl is draw back to each of several 250 mL
Erlenmeyer flasks (E-flasks) before the experiments begins and add
the indicator.
3. Concentration of NaOH in titration (in burette) is determined using
the 0.05 M HCl was prepare above (a minimum of three titrations) ,
firstly prepare 0.05M NaOH , secondly titrate with 0.05 M HCl
above to correct concentration of NaOH prepared may be less or
more than its prepared value 0.05 M NaOH .
4. Samples should be collected from the reactor vessel using a 10 mL
transfer pipette or medical injection at appropriate time intervals to
monitor the rate of reaction. At the start of the reaction samples
should be collected at short time intervals. No more than 6 or 7
samples should be collected during the run because 6 or 7 points
construct the necessary graph .The 10 mL sample should be
discharged into the 250 mL E-flask containing 10 mL of HCl and
indicator. The time of collection shall be taken when one-half of the
sample has been discharged from the pipette or the medical
injection in to the E-flask .
5. The sample is titrated with the calculated base in (3) and the volume
recorded. [5]
Figure 3.2: Withdrew the sample by medical injection, acid with an
indicator in E-flask and the titration unit
29
Figure 3.2: Withdraw the sample by medical injection, acid with
an indicator in E-flask and the titration unit
30
3.4.5 Experiment A: Determination of concentration
dependency factor for caustic soda
Consider − rA = k A C Aa C Bb = k A C NaOH
a b
C Ethyl Acetate − − − Eq (3.3)
Experiment A Concept
1. Using the Method of Excess to determine the order with respect to
one of the reactants. (Three times the concentration) is sufficient in
this experiment. A reaction of this type may be called a pseudo-first
order reaction.
Where:
C A = C NaOH = concentration (in mol/lit) of unreacted NaOH in each
31
Table 3.1: Experiment A Concept Concentration of unreacted NaOH
Time , second t0 t1 t2 t3 t4 tn
− dC A
6. Used method of finite difference to calculate (− rA ) or ( )
dt
( 2.6.2 , Eqs( 2.27 to 2.29))
7. Use Excel program to Plot log-log graph for (−rA ) vs C A
and Trend (Line, power) to get k ′ and a
Experiment A Procedure (Three Batches) :
Isothermal operation at 37.7 0C
Procedure:
1. 0.05 M HCl was prepared and used in the experiment (Standard
acid solution) ,10 mL of it is pipetted into each of several 250 mL
Erlenmeyer flasks (E-flasks) before the experiment began .
2. Concentration of NaOH in titration (in burette) is determined
using the 0.05 M HCl was prepared above (a minimum of three
titrations) , firstly prepare 0.05M NaOH , secondly titrate it with
0.05 M HCl above to correct concentration of NaOH prepared
may be less or more than its prepared value 0.05 M NaOH in
Table(3.2) .
Vacid × M acid = Vbase × M basic − − − − − − − − − − − − − − − − − − − − − Eq (3.9)
32
Table 3.2: Experiment A acid base titration
Standard acid solution Measured base solution
NO(titrations)
Vacid (ml) M acid (mol/lit) Vbase (ml) M base (mol/lit) Average M base (mol/lit)
3. In the reactor, mix 0.5 liter of the 0.1M caustic soda solution with
0.5 liter of the 0.3M ethyl acetate solution at an arbitrary time (t =
0
0) at 37.7 C switch on the stirrer immediately and set it to an
intermediate speed to avoid splashing.
4. Start the timer as soon as you start mixing the reactants.
5. After a certain time interval, use a medical injection to withdraw
10ml sample from the reactor, and immediately quench it with
10ml of excess 0.05M hydrochloric acid (You should have the
quenching acid sample ready before taking the sample from the
reactor) .
6. Add 2 - 3 drops of phenolphthalein to the quenched sample and
back titrate with 0.048544 M NaOH solution until the end point is
detected (in this case a stable pink color) .
7. Record the amount of NaOH used in the titration (V titration.).
8. Repeat steps (5) - (7) every 1 minute for the samples. Take a total
of 6-7samples making sure that you record the time for each new
sample.
9. Calculate experiment A batch (I) volume of NaOH used in the
titration, the results are shown in (Table 3.3).
33
Table 3.3: Experiment A batch (I) volume of NaOH used in the
titration
Volume NaOH
Initial Burette Final Burette
Sample Time (s) used in Titration[Final-
reading (ml) Reading(ml)
Initial](ml)
0 0 0 0 0
1 60 10.3 19.25 8.95
2 120 19.25 29.1 9.85
3 180 29.1 39.15 10.05
4 240 39.15 49.30 10.15
5 300 0 10.2 10.2
6 360 10.2 20.45 10.25
34
Table 3.4: Experiment A batch (I) Concentration of unreacted NaOH
Time Volume NaOH used in titration
Sample # Un reacted NaOH(mol/lit)
(s) (ml)
0 0 0 0.1
1 60 7.95 0.00655312
2 120 9.85 0.00218416
3 180 10.05 0.00121328
4 240 10.15 0.00072784
5 300 10.2 0.00048512
6 360 10.25 0.00024240
= 0.0022998
Interior points:
⎡ dC ⎤ C − C A0 (0.0021842 − 0.1000000)
−⎢ A⎥ = − A120 =− = 0.0008151
⎣ dt ⎦ t =60 2 ∆t 2 × 60
35
Last point:
⎡ dC ⎤ − 3C A240 + 4C A300 − C A360 − 3 × 0.0007278+ 4 × 0.0004851− 0.0002424
−⎢ A⎥ =− =−
⎣ dt ⎦ t =360 2∆t 2 × 60
= 0.0000040
Add column of the rate of reaction NaOH to the (Table 3.4) .
Table 3.5: Experiment A batch (I) rate of reaction of NaOH
0 0 0.1000000 0.0022998
60 8.95 0.0065531 0.0008151
120 9.85 0.0021842 0.0000445
180 10.05 0.0012133 0.0000121
240 10.15 0.0007278 0.0000061
300 10.2 0.0004851 0.0000040
360 10.25 0.0002424 0.0000040
12. Experiment A the three batches had been calculated, the results
are showing in (Table 3.6).
Table 3.6: Experiment A the three batches ( t,vtit,Con,rate) of NaOH
Batch I Batch II Batch III
Time
V( V( V(
(sec) CA − rA CA − rA CA − rA
tit) tit) tit)
0 0 0.1000000 0.0022998 0 0.1 0.002278 0 0.10000000 0.002275
60 8.95 0.0065531 0.0008151 8.8 0.00728128 0.000813 8.75 0.00752400 0.000807
120 9.85 0.0021842 0.0000445 9.8 0.00242688 0.000097 9.65 0.00315504 0.000109
180 10.05 0.0012133 0.0000121 10 0.00145600 0.000028 10.1 0.00097056 0.000040
240 10.15 0.0007278 0.0000061 10.15 0.00072784 0.000016 10.15 0.00072784 0.000008
300 10.2 0.0004851 0.0000040 10.2 0.00048512 0.000008 10.2 0.00048512 0.000008
360 10.25 0.0002424 0.0000040 10.25 0.0002424 0.000004045 10.25 0.00024 0.000004005
36
3.4.6 Experiment B: Determination of concentration
dependency factor for Ethyl Acetate.
Consider − rA = k A C Aa C Bb = k A C NaOH
a b
C Ethyl Acetate − − − Eq (3.3)
Experiment B Concept
1. To determine the reaction order overall. This can be done by running
the experiment as a batch reactor with equal initial concentrations of
both reactants. A minimum of three batch experiments should be run
with equal concentrations of reactants, one at the same temperature of
Experiment A.
2. Perform the experiment with C A0 = C B 0 and measure C A as a function
of time.
3. From the experiment get the volume of NaOH used in the titration .
4. Calculate the concentration (in mol/lit) of unreacted NaOH in each
sample withdrawn from the reactor, the following equation may be
used
Vacid × M acid − Vtit × M base
C A = C NaOH = (mol / litter ) − − − − − − − − − Eq (3.5)
Vsample
Where:
C A = C NaOH = concentration (in mol/lit) of unreacted NaOH in each
37
Table 3.7: Experiment B Concept Concentration of unreacted NaOH
Time , second t0 t1 t2 t3 t4 tn
38
Table 3.8: Experiment B acid base titration
Standard acid solution Measured base solution
NO(titrations)
Vacid (ml) M acid (mol/lit) Vbase (ml) M base (mol/lit) Average M base (mol/lit)
3. In the reactor, mix 0.5 liter of the 0.1M caustic soda solution with
0.5 liter of the 0.1M ethyl acetate solution at an arbitrary time (t =
0) at 37.7 0C . Switch on the stirrer immediately and set it to an
intermediate speed to avoid splashing.
4. Start the timer as soon as you start mixing the reactants.
5. After a certain time interval, use a pipette or medical injection to
withdraw 10ml sample from the reactor, and immediately quench
it with 10ml of excess 0.05M hydrochloric acid (You should have
the quenching acid sample ready before taking the sample from
the reactor) .
6. Add 2 - 3 drops of phenolphthalein to the quenched sample and
back titrate with 0.048544 M NaOH solution until the end point is
detected (in this case a stable pink color) .
7. Record the amount of NaOH used in the titration (V titration.).
8. Repeat steps (5) - (7) every 2 minute for the samples. Take a total
of 6-7samples making sure that you record the time for each new
sample
9. Calculate experiment B batch (I) volume of NaOH used in the
titration ,The results are shown in (Table 3.9)
39
Table 3.9: Experiment B batch (I) volume of NaOH used in the titration
Volume NaOH
Initial Burette Final Burette
Sample Time (s) used in Titration
reading (ml) Reading(ml)
[Final-Initial](ml)
0 0 0 0 0
1 120 0 5.9 5.9
2 240 5.7 13.7 7.8
3 360 13.7 21.7 8
4 480 21.7 30 8.3
5 600 30 38.5 8.5
40
Table 3.10: Experiment B batch (I) Concentration of unreacted NaOH
Time Volume NaOH used in titration
Sample # Un reacted NaOH(mol/lit)
(s) (ml)
0 0 0 0.1
1 120 5.9 0.02135904
2 240 7.8 0.01213568
3 360 8 0.01116480
4 480 8.3 0.00970848
5 600 8.5 0.00873760
6 720 8.7 0.00776672
= 0.0009446
Interior points:
⎡ dC ⎤ C − C A0 (0.01213568 − 0.1000000)
−⎢ A⎥ = − A 240 =− = 0.0003661
⎣ dt ⎦ t =120 2∆t 2 × 120
41
Last point:
⎡ dC ⎤ − 3C A480 + 4C A600 − C A720 − 3 × 0.00970848+ 4 × 0.0087376− 0.00776672
−⎢ A⎥ =− =−
⎣ dt ⎦ t =720 2∆t 2 × 60
= 0.0000081
12. Experiment B the three batches had been calculated ,the results
are showing in (Table3.12):
Table 3.12: Experiment B the three batches ( t,vtit,Con,rate) of NaOH
Batch I Batch II Batch III
Time
V( V(
(sec) CA − rA CA − rA V( tit) CA − rA
tit) tit)
0 0 0.1 0.0009446 0 0.1 0.00100728 0 0.1 0.000967
120 5.9 0.02135904 0.0003661 6.6 0.01796096 0.00036003 6.1 0.02038816 0.000360
240 7.8 0.01213568 0.0000425 7.5 0.01359200 0.00002427 7.5 0.01359200 0.000040
360 8 0.0111648 0.0000101 7.8 0.01213568 0.00001011 8.1 0.01067936 0.000016
480 8.3 0.00970848 0.0000101 8 0.01116480 0.00001011 8.3 0.00970848 0.000006
600 8.5 0.0087376 0.0000081 8.3 0.00970848 0.00001214 8.4 0.00922304 0.000007
13. Use Excel program to Plot log-log graph for (−rA ) vs C A and
Trend (power) to get k ′ and α : The results are shown in Figures
(4.7 to 4.12)
14. Evaluate b = α − a the order with respect to Ethyl acetate.
42
3.4.7 Experiment C: Determination of dependency factor for
temperatures.
Experiment C Concept
1. After determined the overall reaction order in the Experiment B at
run with equal initial concentrations of both reactants at constant
1/CA = 0.2486*t + 10
200.00
R2 = 1
150.00
1/CA
100.00
Rate constant
50.00
0.00
0 200 400 600 800
tim e(sec)
43
Experiment C: Procedure (Three Batches):
I. Isothermal Operation at 31.2 0C
Procedure:
1. 0.05 M HCl was prepared used in the experiment (Standard acid
solution) ,10 mL of it is pipetted into each of several 250 mL
Erlenmeyer flasks (E-flasks) before the experiment began .
2. Concentration of NaOH in titration (in burette) is determined
using the 0.05 M HCl was prepared above (a minimum of three
titrations) , firstly prepare 0.05M NaOH , secondly titrate it with
0.05 M HCl above to correct concentration of NaOH prepared
may be less or more than its prepared value 0.05 M NaOH in
(Table3.13) .
Vacid × M acid = Vbase × M basic − − − − − − − − − − − − − − − − − − − − − Eq (3.9)
3. In the reactor, mix 0.5 liter of the 0.1M caustic soda solution with
0.5 liter of the 0.1M ethyl acetate solution at an arbitrary time (t =
0) at 31.2 0C . Switch on the stirrer immediately and set it to an
intermediate speed to avoid splashing.
4. Start the timer as soon as you start mixing the reactants.
5. After a certain time interval, use a pipette or medical injection to
withdraw 10ml sample from the reactor, and immediately quench
it with 10ml of excess 0.05M hydrochloric acid (You should have
the quenching acid sample ready before taking the sample from
the reactor) .
44
6. Add 2 - 3 drops of phenolphthalein to the quenched sample and
back titrate with 0.048544 M NaOH solution until the end point is
detected (in this case a stable pink color) .
7. Record the amount of NaOH used in the titration (V titration.).
8. Repeat steps (5) - (7) every 2 minute for the samples. Take a total
of 6-7samples making sure that you record the time for each new
sample.
9. Calculation Experiment C batch (I) at 31.2 0C . The results are
shown in (Table 3.14)
Table 3.14: Experiment C batch (I) volume of NaOH used in the
titration
Volume NaOH
Initial Burette Final Burette
Sample Time (s) used in Titration
reading (ml) Reading(ml)
[Final-Initial](ml)
0 0 0 0 0
1 120 0 5.1 5.1
2 240 5.1 12 6.9
3 360 12 19.5 7.5
4 480 19.5 27.6 8.1
5 600 27.6 36.3 8.7
45
[C NaOH ]t =360 = 10 × 0.05 − 7.5 × 0.048544 = 0.013592
10
46
II. Isothermal Operation at 37.7 0C
Procedure:
1. 0.05 M HCl was prepared used in the experiment (Standard acid
solution) ,10 mL of it is pipetted into each of several 250 mL
Erlenmeyer flasks (E-flasks) before the experiment began .
2. Concentration of NaOH in titration (in burette) is determined
using the 0.05 M HCl was prepared above (a minimum of three
titrations) , firstly prepare 0.05M NaOH , secondly titrate it with
0.05 M HCl above to correct concentration of NaOH prepared
may be less or more than its prepared value 0.05 M NaOH in
(Table 3.17) .
Vacid × M acid = Vbase × M basic − − − − − − − − − − − − − − − − − − − − − Eq(3.9)
3. In the reactor, mix 0.5 liter of the 0.1M caustic soda solution with
0.5 liter of the 0.1M ethyl acetate solution at an arbitrary time (t =
0) at 37.7 0C . Switch on the stirrer immediately and set it to an
intermediate speed to avoid splashing.
4. Start the timer as soon as you start mixing the reactants.
5. After a certain time interval, use a pipette or medical injection to
withdraw 10ml sample from the reactor, and immediately quench
it with 10ml of excess 0.05M hydrochloric acid (You should have
the quenching acid sample ready before taking the sample from
the reactor) .
47
6. Add 2 - 3 drops of phenolphthalein to the quenched sample and
back titrate with 0.048544 M NaOH solution until the end point is
detected (in this case a stable pink color) .
7. Record the amount of NaOH used in the titration (V titration.).
8. Repeat steps (5) - (7) every 2 minute for the samples. Take a total
of 6-7samples making sure that you record the time for each new
sample.
9. Calculation Experiment Three batch (II) at 37.7 0C . The results
are shown in (Table 3.18).
Table 3.18: Experiment C batch (II) volume of NaOH used in titration
Volume NaOH
Initial Burette Final Burette
Sample Time (s) used in Titration
reading (ml) Reading(ml)
[Final-Initial](ml)
0 0 0 0 0
1 120 0 6 6
2 240 6 13.5 7.5
3 360 13.5 21.3 7.8
4 480 21.3 29.6 8.3
5 600 29.6 38 8.4
48
[C NaOH ]t =480 = 10 × 0.05 − 8.3 × 0.048544 = 0.00970848
10
get rate constant , The results are shown in Figures (4.15 to 4.16)
49
III. Isothermal Operation at 45.5 0C
Procedure:
1. 0.05 M HCl was prepared used in the experiment (Standard acid
solution) ,10 mL of it is pipettd into each of several 250 mL
Erlenmeyer flasks (E-flasks) before the experiment began .
2. Concentration of NaOH in titration (in burette) is determined
using the 0.05 M HCl was prepared above (a minimum of three
titrations) , firstly prepare 0.05M NaOH , secondly titrate it with
0.05 M HCl above to correct concentration of NaOH prepared
may be less or more than its prepared value 0.05 M NaOH in
(Table3.21) .
Vacid × M acid = Vbase × M basic − − − − − − − − − − − − − − − − − − − − − Eq(3.9)
3. In the reactor, mix 0.5 liter of the 0.1M caustic soda solution with
0.5 liter of the 0.1M ethyl acetate solution at an arbitrary time (t =
0) at 45.5 0C . Switch on the stirrer immediately and set it to an
intermediate speed to avoid splashing.
4. Start the timer as soon as you start mixing the reactants.
5. After a certain time interval, use a pipette or medical injection to
withdraw 10ml sample from the reactor, and immediately quench
it with 10ml of excess 0.05M hydrochloric acid (You should have
the quenching acid sample ready before taking the sample from
the reactor) .
50
6. Add 2 - 3 drops of phenolphthalein to the quenched sample and
back titrate with 0.048544 M NaOH solution until the end point is
detected (in this case a stable pink color) .
7. Record the amount of NaOH used in the titration (V titration.).
8. Repeat steps (5) - (7) every 2 minute for the samples. Take a total
of 6-7samples making sure that you record the time for each new
sample.
9. Calculation Experiment Three batch (III) at 45.5 0C . The results
are shown in (Table 3.22)
Table 3.22: Experiment C batch (III) volume of NaOH used in
titration
Volume NaOH
Initial Burette Final Burette
Sample Time (s) used in Titration
reading (ml) Reading(ml)
[Final-Initial](ml)
0 0 0 0 0
1 120 0 6.6 6.6
2 240 6.6 14.4 7.8
3 360 14.4 23 8.6
4 480 23 31.8 8.8
5 600 31.8 41 9.2
51
[C NaOH ]t =360 = 10 × 0.05 − 8.6 × 0.048544 = 0.00825216
10
1
12. Use Excel program to plot between vs t and Trend (Line) to
CA
get rate constant. The results are shown in Figures (4.17 to 4.18)
52
CHAPTER FOUR
RESULTS & DISCUSSION
4.1. Results
Results for experiments (A,B,C) are showing in figures (4.1 to 4.18)
0.10
0.09
Concentration 0f (NaOH) (mol/lit)
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0 60 120 180 240 300 360
Tim e(sec)
Experimental literature
53
Experim ent A batch (I)
-dCA/dt = 0.0751*CA1.2283
R2 = 0.9006
0.000001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001 0.0001
Concentration 0f (NaOH) (m ol/lit)
0.09
Concentration 0f (NaOH) (mol/lit)
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0 60 120 180 240 300 360
Tim e(sec)
Experimental literaturel
54
Figure 4.4 Shows Experiment A (isothermal at 37.70C) batch (II) Excel
log - log plot for experimental rate of reaction of caustic soda versus its
concentration from (Table 3.6) .
Experim ent A batch (II) -dCA/dt = 0.0619*CA1.1316
R2 = 0.9296
0.000001
rate of reaction (NaOH) (mol/lit.sec)
0.00001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001 0.0001
Concentration 0f (NaOH) (m ol/lit)
55
Experim e nt A batch (III)
0.10
0.09
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0.00
0 60 120 180 240 300 360
Tim e (s e c)
Experimental literature
1.1406
Experim ent A batch (III) -dCA/dt = 0.0645*CA
2
R = 0.918
0.000001
rate of reaction (NaOH) (mol/lit.sec)
0.00001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001 0.0001
Concentration 0f (NaOH) (m ol/lit)
56
4.1.2. Experiment B (isothermal at 37.70C)
Figure 4.7 Shows Experiment B (isothermal at 37.70C) batch (I) the
change of concentration of caustic soda versus time for the simulated
literature values from Appendix B versus the experimental values from
(Table 3.12).
0.1
0.09
0.08
Concentration 0f (NaOH) (mol/lit)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600 720
Tim e(sec)
Experimental literature
57
2.0332
Experim ent B batch (I) -dCA/dt = 0.184CA
2
R = 0.8299
0.000001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
0.09
0.08
Concentration 0f (NaOH) (mol/lit)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600 720
Tim e (s e c)
Experimental literature
58
Figure 4.10 Shows Experiment B (isothermal at 37.70C) batch (II)
Excel log - log plot for experimental rate of reaction of caustic soda
versus its concentration from (Table 3.12) .
0.00001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
59
Expe rim e nt B batch (III)
0.1
0.09
0.08
0.06
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600 720
Tim e(s e c)
Experimental literature
0.00001
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
60
4.1.3. Experiment C (non isothermal)
Figure 4.13 Shows Experiment C (at 31.20C) batch (I) the change of
concentration of caustic soda versus time for the simulated literature
values versus the experimental values from (Table 3.16) .
0.09
0.08
Concentration 0f (NaOH) (mol/lit)
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600
Tim e(se c)
Experimental Actual
Figure 4.13: Experiment C (at 31.20C) batch (I) Concentration time data
from Experimental and literature values from (Table 3.16) .
Figure 4.14 Shows Experiment C (at 31.20C) batch (I) Excel plot for
inverse experimental and actual concentration on literature of caustic
soda versus time from (Table 3.16).
61
Experiment C batch (I) at 31.2 C
120
Actual :1/CA = 0.1667*t + 10
100 R2 = 1
Exp:1/CA = 0.1822*t + 10
1 /C A (li t/m o l )
80
R2 = 0.9695
60
40
20
0
0 100 200 300 400 500 600 700
time(sec)
Figure 4.14: Experiment C (at 31.2 0C) batch (I) Excel program to plot
1/CA vs t , from (Table 3.16) .
Figure 4.15 Shows Experiment C (at 37.70C) batch (II) the change of
concentration of caustic soda versus time for the simulated literature
values versus the experimental values from (Table 3.20).
0.1
0.09
0.08
Concentration 0f (NaOH) (mol/lit)
0.07
Exp
0.06 Acual
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600
Tim e(se c)
62
Figure 4.16 Shows Experiment C (at 37.70C) batch (II) Excel plot for
inverse experimental and actual concentration on literature of caustic
soda versus time from (Table 3.20).
120
100
80
60
40
20
0
0 100 200 300 400 500 600 700
time (sec)
Expremental Actual Linear (Actual) Linear (Expremental)
Figure 4.16: Experiment C (at 37.70C) batch (II) Excel program to plot
1/CA vs t from (Table 3.20) .
Figure 4.17 Shows Experiment C (at 45.50C) batch (III) the change of
concentration of caustic soda versus time for the simulated literature
values versus the experimental values from (Table 3.24) .
63
Experim e nt C batch (III) at 45.5 c
0.1
0.09
0.08
0.06
0.05
0.04
0.03
0.02
0.01
0
0 120 240 360 480 600
Tim e(s ec)
Experimental Actual
Figure 4.18 Shows Experiment C (at 45.50C) batch (III) Excel plot for
inverse experimental and actual concentration on literature of caustic
soda versus time from (Table 3.24) .
200
1/CA (lit/mol)
150
100
50
0
0 200 400 600 800
time (sec)
Figure 4.18: Experiment C (at 45.50C) batch (III) Excel program to plot
1/CA vs t from (Table 3.24).
64
4.2. Discussion
4.2.1. Discussion Experiment A (isothermal at 37.70C)
The results of order with respect to caustic soda (a) is showing in
Figures (4.2 ,4.4 and 4.6) and (Table 4.1).
Table 4.1: Experiment A average order with respect to (NaOH)
NO Of reaction order with respect to Average reaction order with respect
Batches (NaOH) to (NaOH)
1 1.2283
2 1.1316 1.16683
3 1.1406
65
determining the constants ai , one has only to differentiate Eq(2.30) to
get Eq(2.31) .
The program was used poly math 6.1 the experiment A the three
batches are shown below:
Experiment A batch (I)
1. Enter the concentration time data from (Table 3.6) and choose the
order of the polynomial 6 is show in (Figure4.19) .
Where t = time (sec) , CA= concentration of NaOH
Figure 4.19: Experiment A batch (I) data input to poly math program
66
2. Poly math report :
POLYMATH Report
Polynomial Regression
a0 0.1 0
a1 -0.0036027 0
a2 5.226E-05 0
a3 -3.821E-07 0
a4 1.486E-09 0
a5 -2.933E-12 0
a6 2.305E-15 0
t d(CA)/d(t)
0 -0.0036027
60 -0.0003524
120 1.254E-05
180 -3.075E-05
240 1.463E-05
300 -4.416E-05
360 0.0002008
General
Degree of polynomial = 6
Regression including a free parameter
Number of observations = 7
67
Statistics
R^2 1.
R^2adj 0
Rmsd 3.412E-12
Variance 1.0E+99
Graph
68
3. From report the polynomial equation is accurate for negative
derivatives points and choose the first negative derivatives points at
the (Table 4.2) and excel plot (-dCA/dt) of (NaOH) versus its
concentration in (Table 4.2) showing in (Figure4.20) .
Table 4.2: Poly math batch (I) first negative derivative points
polynomial Rate of
Time (s) CA equation reaction
[dCA/dt] [- dCA/dt]
0 0.1000000 -0.0036027 0.0036027
60 0.0065531 -0.0003524 0.0003524
180 0.0012133 -3.075E-05 3.075E-05
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
69
Experiment A batch (II)
1. Enter the concentration time data from (Table 3.6) and choose the
order of the polynomial 6 is show in (Figure 4.21).
Where t = time(sec) , CA= concentration of NaOH
Figure 4.21: Experiment A batch (II) data input to poly math program
70
2. Poly math report :
POLYMATH Report
Polynomial Regression
a0 0.1 0
a1 -0.0035332 0
a2 5.054E-05 0
a3 -3.65E-07 0
a4 1.404E-09 0
a5 -2.744E-12 0
a6 2.139E-15 0
t d(CA)/d(t)
0 -0.0035332
60 -0.0003646
120 1.072E-05
180 -3.196E-05
240 9.641E-06
300 -3.776E-05
360 0.0001744
General
Degree of polynomial = 6
Regression including a free parameter
Number of observations = 7
71
Statistics
R^2 1.
R^2adj 0
Rmsd 3.2E-12
Variance 1.0E+99
Graph
72
3. From report the polynomial equation is accurate for negative
derivatives points and choose the first negative derivatives points at
the Table 4.3 and excel plot (-dCA/dt) of (NaOH) versus its
concentration in Table 4.3 showing in Figure 4.22.
Table 4.3: Poly math batch (II) first negative derivative points
polynomial Rate of
Time (s) CA equation reaction
[dCA/dt] [- dCA/dt]
0 0.1 -0.0035332 0.0035332
60 0.00728128 -0.0003646 0.0003646
180 0.001456 -3.196E-05 3.196E-05
1.0888
Experiment A batch(II) -dCA/dt = 0.0509CA
2
R = 0.9755
0.00001
rate of reaction (NaOH)
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
73
Experiment A batch (III)
1. Enter the concentration time data from (Table 3.6) and choose the
order of the polynomial 6 is show in (Figure 4.23).
Where t = time(sec) , CA= concentration of NaOH
Figure 4.23: Experiment A batch (III) data input to poly math program
74
2. Poly math report :
POLYMATH Report
Polynomial Regression
a0 0.1 0
a1 -0.0036539 0
a2 5.481E-05 0
a3 -4.151E-07 0
a4 1.666E-09 0
a5 -3.375E-12 0
a6 2.71E-15 0
t d(CA)/d(t)
0 -0.0036539
60 -0.000326
120 8.765E-06
180 -4.045E-05
240 2.596E-05
300 -6.034E-05
360 0.000269
General
Degree of polynomial = 6
Regression including a free parameter
Number of observations = 7
75
Statistics
R^2 1.
R^2adj 0
Rmsd 3.902E-12
Variance 1.0E+99
Graph
76
3. From report the polynomial equation is accurate for negative
derivatives points and choose the first negative derivatives points at
the (Table 4.4) and excel plot (-dCA/dt) of (NaOH) versus its
concentration in (Table 4.4) showing in (Figure 4.24).
Table 4.4: poly math batch (III) first negative derivative points
polynomial Rate of
Time (s) CA equation reaction
[dCA/dt] [- dCA/dt]
0 0.1 -0.0036539 0.0036539
60 0.007449505 -0.000326 0.000326
180 0.00096095 -4.045E-05 4.045E-05
0.9678
Experiment A batch(III) -dCA/dt = 0.0349CA
2
R = 0.9993
0.00001
rate of reaction (NaOH)
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001 0.0001
Concentration 0f (NaOH) (m ol/lit)
77
4. Summary of discussion of experiment A
Table 4.5: Summary of discussion of experiment A
CHEMCAD
NO of
Numerical Method average Appendix B Actual average Poly math average
Batches
values
1 1.2283 1.007 1.0581
2 1.1316 1.16683 1.007 1.007 1.0888 1.0382
3 1.1406 1.007 0.9678
b= 2.0144-1.16683 = 0.8476
2. Summary of discussion of experiment B
Table 4.7: Summary of discussion of experiment B
CHEMCAD
NO of
Numerical Method average Appendix B Actual average
Batches
values
1 2.0332 2.0011
2 1.9821 2.0144 2.0011 2.0011
3 2.0279 2.0011
78
4.2.3. Discussion Experiment C
The results of rate constant for second order with respect to caustic soda
are shown in Figures(4.13 to 4.18) and (Table 4.8).
Table 4.8: Experiment C rate constant for second order reaction with
respect to (NaOH)
Error
NO Of Temperatures rate constant for second order Literature
%
Batches (0C) reaction with respect to (NaOH) value
79
From (Table 4.9) a new value of reactor temperature and value of rate
constant from literature (Appendix C , Table C.1 ) ,the result shown in
(Table 4.10).
Table 4.10: Experiment C reason (1) rate constant for second order
reaction with respect to (NaOH)
New Literature
NO of Temperatures rate constant for second order Error %
0
value according
batches ( C) reaction with respect to (NaOH)
to reason(1)
Batch (I) 31.3 0.1822 0.1677 8.65
Batch (II) 38.12 0.2751 0.2547 8.01
Batch (III) 45.22 0.3806 0.3865 -1.527
80
1) Calculation Activation Energy from Experiment C (Table 4.8)
and literature from Appendix C .
Table 4.11: Activation Energy Experiment C and Actual or literature
value from Appendix C
Temperature 1/T Exp Ac
Measurement Exp(k) Ac (k) T(0K) 0
[C] (1/ K) ln(k) ln(k)
Batch (I) 31.2 0.1822 0.1667 304.35 0.003286 -1.70265 -1.7915595
Batch (II) 37.7 0.2751 0.2486 310.85 0.003217 -1.29062 -1.3919101
Batch (III) 45.5 0.3806 0.3932 318.65 0.003138 -0.96601 -0.9334369
-2 Activity Energy
-1.5
ln(K)
-1
-0.5
0
0.0031 0.00315 0.0032 0.00325 0.0033
(1/T)
81
2) Activation Energy from Experiment C batch (I) and batch (II)
Experim ental ln(k) = -5997.1*(1/T) + 18.002 Actual ln(K) = -5819.8*(1/T) + 17.33
R2 = 1 R2 = 1
-2 Activity Energy
ln(K) -1.5
-1
-0.5
0
0.0031 0.00315 0.0032 0.00325 0.0033
(1/T)
Figure 4.26: Excel plot Activation Energy for Experiment C batch(I) and
batch(II) from (Table 4.11).
E Exp Jole Jole
= −5997.1 0k ⇒ E Exp = −5997.10 k × 8.314 0
= −49859.8894
R mol. k mol
82
4) The comprehensive rate equation
Described by Eq (2.13)
− rA = k A C Aa C Bb − − − − − − − − − − − − − − − − − − − − − Eq(2.13)
By use Eq(2.17)
E 1 1
( − )
k A [T ] = k A [To ] e R To T
− − − − − − − − − − − − − − − − − Eq(2.17)
83
CHAPTER FIVE
CONCLUSION & RECOMMENDATION
5.1 Conclusion
1. The pilot - scale batch reactor has been refurbished with a minimal
cost.
2. Use of the unit with the water bath has provided better temperature
control compared with using the heater and cold water around the
jacket of reactor.
3. A saponification reaction provides a safe option for use as a case
study.
4. Reaction kinetics is in line with literature.
5. In experiment A access material (Three times the concentration) is
sufficient in this experiment. The use of the Polynomial Fit method
(poly math software) provided better than finite difference method.
6. In experiment B (equal molar) the use of finite difference method to
calculate the derivative is sufficient.
5.2 Recommendations
1. Automation for batch reactor through adding hardware and software
components such as lab view, Matlab.
2. To add experiment to fifth year undergraduate students to reinforce
their experimental skills.
84
REFERENCES
1. Fogler, S. H.; “Elements of Chemical Reaction Engineering,”
Prentice Hall, 4rd Edition (2006)
2. A. SARATH BABU,“BATCH REACTOR - Interpretation of rate
data”, (http://www.engin.umich.edu/3.Batch_reactor.ppt)
3. Tsujikawa, Hiroo, and Inoue, Hakuai. “The Reaction Rate of Alkaline
Hydrolysis of Ethyl Acetate”, Bulletin of the Chemical Society of
Japan, 39: 1837-1842
4. www.csupomona.edu/~tknguyen/che435/Notes/files_2Experiments_
Homogenuous_Batch_Reactor.pdf
5. UNIVERSITY OF MINNESOTA DULUTH - DEPARTMENT OF
CHEMICAL ENGINEERING- ChE 3211-4211,” BATCH
REACTOR “, exbatrea.pdf
85
APPENDIXES
Common
Caustic soda, soda lye
synonyms
Formula NaOH
86
Eye contact: Immediately flush the eye with plenty of water.
Continue for at least ten minutes and call for immediate
medical help. Skin contact: Wash off with plenty of water.
Emergency Remove any contaminated clothing. If the skin reddens or
appears damaged, call for medical aid. If swallowed: If the
patient is conscious, wash out the mouth well with water. Do
not try to induce vomiting. Call for immediate medical help
Common Ethyl ethanoate , acetic acid ethyl ester, ethanoic acid ethyl
synonyms ester
Formula CH3COOC2H5
87
Melting point: -84 C
Boiling point: 77 C
Water solubility: soluble
Specific gravity: 0.9
Flash point: -4 C
Principal
Ethyl acetate is very flammable
hazards
88
Appendix B : CHEMCAD Software (Saponification Reaction
Simulation)
1. Experiment A access material isothermal operation
37.7 0C
89
Table B .1: CHEMCAD, Experiment A concentration time data combine
with finite difference and Excel
Plot Title: Experiment A at 37.7 degree
Set Name: Sodium Hydroxide
61
Data Points:
90
Experim ent A at 37.7
-dCA/dt = 0.0545xCA1.0078
R2 = 0.9999
1E-11
1E-10
1E-09
Acual
P (A l)
91
Table B .2: CHEMCAD, Experiment B concentration time data combine
with finite difference and Excel
Plot Title: Experiment B at 37.7 degree
Set Name: Sodium Hydroxide
121
Data Points:
92
Table B.2: continuous
Plot Title: Experiment B at 37.7 degree
Set Name: Sodium Hydroxide
121
Data Points:
93
Experim ent B at 37.7
-dCA/dt = 0.2463CA2.0011
R2 = 1
0.000001
0.00001
rate of reaction (NaOH)
0.0001
0.001
0.01
0.1
1
1 0.1 0.01 0.001
Concentration 0f (NaOH) (m ol/lit)
Acual
P (A l)
94
Appendix C: Rate constant versus Temperatures in
Saponification Literature Values
Table C.1: Rate constant vs Temperatures Saponification Literature
Values
Temp Temp Temp Temp Temp
k k k k k
(c) (c) (c) (c) (c)
25.0 0.1120 28.3 0.1387 31.6 0.1709 34.9 0.2097 38.2 0.2562
25.1 0.1127 28.4 0.1396 31.7 0.1720 35.0 0.2110 38.3 0.2578
25.2 0.1135 28.5 0.1405 31.8 0.1731 35.1 0.2123 38.4 0.2593
25.3 0.1142 28.6 0.1414 31.9 0.1742 35.2 0.2136 38.5 0.2609
25.4 0.1150 28.7 0.1423 32.0 0.1753 35.3 0.2149 38.6 0.2625
25.5 0.1157 28.8 0.1432 32.1 0.1764 35.4 0.2163 38.7 0.2640
25.6 0.1165 28.9 0.1441 32.2 0.1775 35.5 0.2176 38.8 0.2656
25.7 0.1172 29.0 0.1450 32.3 0.1786 35.6 0.2189 38.9 0.2672
25.8 0.1180 29.1 0.1460 32.4 0.1797 35.7 0.2203 39.0 0.2688
25.9 0.1188 29.2 0.1469 32.5 0.1808 35.8 0.2216 39.1 0.2704
26.0 0.1196 29.3 0.1478 32.6 0.1819 35.9 0.2230 39.2 0.2720
26.1 0.1203 29.4 0.1488 32.7 0.1831 36.0 0.2243 39.3 0.2737
26.2 0.1211 29.5 0.1497 32.8 0.1842 36.1 0.2257 39.4 0.2753
26.3 0.1219 29.6 0.1507 32.9 0.1854 36.2 0.2271 39.5 0.2769
26.4 0.1227 29.7 0.1516 33.0 0.1865 36.3 0.2284 39.6 0.2786
26.5 0.1235 29.8 0.1526 33.1 0.1877 36.4 0.2298 39.7 0.2803
26.6 0.1243 29.9 0.1536 33.2 0.1889 36.5 0.2312 39.8 0.2819
26.7 0.1251 30.0 0.1545 33.3 0.1900 36.6 0.2326 39.9 0.2836
26.8 0.1259 30.1 0.1555 33.4 0.1912 36.7 0.2341 40.0 0.2853
26.9 0.1267 30.2 0.1565 33.5 0.1924 36.8 0.2355 40.1 0.2870
27.0 0.1276 30.3 0.1575 33.6 0.1936 36.9 0.2369 40.2 0.2887
27.1 0.1284 30.4 0.1585 33.7 0.1948 37.0 0.2384 40.3 0.2904
27.2 0.1292 30.5 0.1595 33.8 0.1960 37.1 0.2398 40.4 0.2921
27.3 0.1301 30.6 0.1605 33.9 0.1972 37.2 0.2413 40.5 0.2939
27.4 0.1309 30.7 0.1615 34.0 0.1984 37.3 0.2427 40.6 0.2956
27.5 0.1317 30.8 0.1626 34.1 0.1997 37.4 0.2442 40.7 0.2974
27.6 0.1326 30.9 0.1636 34.2 0.2009 37.5 0.2457 40.8 0.2991
27.7 0.1334 31.0 0.1646 34.3 0.2021 37.6 0.2471 40.9 0.3009
27.8 0.1343 31.1 0.1656 34.4 0.2034 37.7 0.2486 41.0 0.3027
27.9 0.1352 31.2 0.1667 34.5 0.2046 37.8 0.2501 41.1 0.3045
28.0 0.1360 31.3 0.1677 34.6 0.2059 37.9 0.2517 41.2 0.3063
28.1 0.1369 31.4 0.1688 34.7 0.2072 38.0 0.2532 41.3 0.3081
28.2 0.1378 31.5 0.1699 34.8 0.2085 38.1 0.2547 41.4 0.3099
95
Table C.1: Continuous
Temp Temp Temp Temp Temp
k k k k k
(c) (c) (c) (c) (c)
41.5 0.3117 44.8 0.3777 48.1 0.4558 51.4 0.5480 54.7 0.6565
41.6 0.3136 44.9 0.3799 48.2 0.4584 51.5 0.5511 54.8 0.6600
41.7 0.3154 45.0 0.3821 48.3 0.4610 51.6 0.5541 54.9 0.6636
41.8 0.3173 45.1 0.3843 48.4 0.4636 51.7 0.5572 55.0 0.6672
41.9 0.3191 45.2 0.3865 48.5 0.4662 51.8 0.5603 55.1 0.6708
42.0 0.3210 45.3 0.3887 48.6 0.4689 51.9 0.5634 55.2 0.6744
42.1 0.3229 45.4 0.3910 48.7 0.4715 52.0 0.5665 55.3 0.6781
42.2 0.3248 45.5 0.3932 48.8 0.4742 52.1 0.5696 55.4 0.6818
42.3 0.3267 45.6 0.3955 48.9 0.4768 52.2 0.5727 55.5 0.6854
42.4 0.3286 45.7 0.3977 49.0 0.4795 52.3 0.5759 55.6 0.6891
42.5 0.3305 45.8 0.4000 49.1 0.4822 52.4 0.5791 55.7 0.6929
42.6 0.3325 45.9 0.4023 49.2 0.4849 52.5 0.5823 55.8 0.6966
42.7 0.3344 46.0 0.4046 49.3 0.4876 52.6 0.5855 55.9 0.7004
42.8 0.3364 46.1 0.4069 49.4 0.4904 52.7 0.5887 56.0 0.7041
42.9 0.3383 46.2 0.4093 49.5 0.4931 52.8 0.5919 56.1 0.7079
43.0 0.3403 46.3 0.4116 49.6 0.4959 52.9 0.5952 56.2 0.7117
43.1 0.3423 46.4 0.4140 49.7 0.4987 53.0 0.5984 56.3 0.7156
43.2 0.3443 46.5 0.4163 49.8 0.5015 53.1 0.6017 56.4 0.7194
43.3 0.3463 46.6 0.4187 49.9 0.5043 53.2 0.6050 56.5 0.7233
43.4 0.3483 46.7 0.4211 50.0 0.5071 53.3 0.6083 56.6 0.7272
43.5 0.3504 46.8 0.4235 50.1 0.5099 53.4 0.6117 56.7 0.7311
43.6 0.3524 46.9 0.4259 50.2 0.5128 53.5 0.6150 56.8 0.7350
43.7 0.3544 47.0 0.4283 50.3 0.5156 53.6 0.6184 56.9 0.7389
43.8 0.3565 47.1 0.4308 50.4 0.5185 53.7 0.6218 57.0 0.7429
43.9 0.3586 47.2 0.4332 50.5 0.5214 53.8 0.6251 57.1 0.7468
44.0 0.3607 47.3 0.4357 50.6 0.5243 53.9 0.6286 57.2 0.7508
44.1 0.3628 47.4 0.4382 50.7 0.5272 54.0 0.6320 57.3 0.7549
44.2 0.3649 47.5 0.4406 50.8 0.5301 54.1 0.6354 57.4 0.7589
44.3 0.3670 47.6 0.4431 50.9 0.5331 54.2 0.6389 57.5 0.7629
44.4 0.3691 47.7 0.4457 51.0 0.5360 54.3 0.6424 57.6 0.7670
44.5 0.3712 47.8 0.4482 51.1 0.5390 54.4 0.6459 57.7 0.7711
44.6 0.3734 47.9 0.4507 51.2 0.5420 54.5 0.6494 57.8 0.7752
44.7 0.3755 48.0 0.4533 51.3 0.5450 54.6 0.6529 57.9 0.7793
96